CN103289558B - A kind of ultraviolet-curing paint for steel surface and preparation method - Google Patents
A kind of ultraviolet-curing paint for steel surface and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of free radical initiation type ultraviolet-curing paint for steel protection, be suitable for the short-term protection of steel product, the steel of particularly band rust operation.Each component and weight percentage are: 36-55 parts by weight of polyurethane origoester acrylate, 35-50 parts by weight of acrylic acid esters monomer, 1-3 part by weight of metal adhesion promoter, 1-3 weight part non-reactive sticking power promotes resin, the agent of 1-2.5 weight part corrosion contacting permeation, the auxiliary agent of 3-10 weight part light trigger and 0.1-1 weight part.The present invention introduces non-reacted resin and corrosion permeate agent originally in photo-cured coating system, efficiently solves steel tube surface greasy dirt rusty stain to the disadvantageous effect of photo-cured coating sticking power.
Description
Technical field
The present invention relates to ultraviolet-curing paint field, particularly one is outer field for steel, free radical initiation type ultraviolet-curing paint and preparation method thereof.
Background technology
In order to prevent steel pipe and steel product from depositing and in transportation, corrosion occurring, reduce quality product.Usually protected at its external coating slushing oil or coating.Rust proof paint at present for steel short-term rust prevention has mineral oil origin, alkyd paint, vinylformic acid baking vanish, powder coating and water-borne coatings.(research of Wang Hangkai, steel pipe UV ultra-violet curing spraying machine gordian technique, Zhejiang Polytechnical University's master thesis)
There is many drawbacks in these traditional rust proof paints.Such as, mineral oil origin slushing oil surface is greasy, easily adheres to workman's clothes or other article, easily pollute in the process of packing carrying; The solidification of alcohol acids oil paint is undertaken by aerial oxypolymerization usually, generally needing to install a baking-curing stove additional at production line and accelerates solidification, even so also usually needing 15min to complete solidification to accelerate solidification.This adds energy consumption on the one hand, reduce production efficiency on the other hand, and the solvent of discharging in baking-curing process is to environment; There is long, the shortcoming such as energy consumption is high time of drying equally in vinylformic acid baking vanish and powder coating; Water-borne coatings can overcome the pollution problem that oil paint causes due to solvent evaporates, but moisture evaporation wherein will be made in water-borne coatings drying process to go out, and needs the baking time more grown or higher storing temperature, also unsatisfactory from the viewpoint of energy consumption.The damage of water-borne coatings paint film is many on the other hand, and the non-finish-drying of coating causes steel pipe paint film damage in transmission, packing, transit link, and then causes the too early corrosion of injury region.
Ultraviolet-curing paint, compared with traditional baking-curing or oxygen curable coating, has quick solidifying (a few second), pollutes less, the advantage such as energy-conservation and applicable production line balance, is widely used in every field.(Wei Jie, " photo-cured coating ", P4-5).Ultraviolet-curing paint is made up of light trigger, reactive monomer, oligopolymer etc., curing mechanism is the irradiation that light trigger accepts UV-light, produces primary group of free radicals, primary group of free radicals causes photoactive monomer again and oligopolymer generation chain polymerization reacts and solidifies.
Along with the Application and Development of various photo-cured coating, chemical engineering teachers find, one of key issue of ultraviolet-curing paint formulating of recipe how to improve the sticking power between film and various base material, wherein especially with comparatively difficult to the attachment of metal base.This is because: photo-cured coating curing speed is fast on the one hand, and during acrylic ester monomer polymerization, volumetric shrinkage is excessive, and the internal stress that when making to solidify, paint film produces has little time release; Between metal base and coating, the formation of physics chemical action is comparatively difficult on the other hand, does not have non-metallic substrate easy.Generally improve its sticking power by adding adhesion promoter, special base material is then needed consider the various factors (research and development of metal ultraviolet-curing paint affecting sticking power, Zhong Jingxiang, the 49th in December, 2011 volume l2 phase, Shanghai coating).The adhesion promoter of common metallic paint comprises the (Yang Jianwen such as acid phosphoric acid ester, long chain mercaptans, silane coupling agent, titanate coupling agent of the resin of band carboxyl, carboxylic acrylate monomer, acroleic acid esterification, photo-cured coating and application, Chemical Industry Press, P200), adhesion promoter can play the function served as bridge connecting base material and coating, thus improves the sticking power of coating and base material.
But, the prerequisite of proving effective above by the method for adding adhesion promoter raising photo-cured coating and metal base sticking power is that base material will through surface treatment, after solvent cleaning, mechanical grinding and chemical treatment are carried out to base material, base material after treatment surface tissue state changes, surface free energy improves, and is conducive to adhesion promoter and plays effectiveness that (recklessly fly, ultraviolet-curing paint is to the research of metal base sticking power, plating and decoration, 18 volumes the 2nd phase in 1999).Surface treatment is the first element guaranteeing paint adhesion, and this point is the common recognition of insider.
But during actual production, on steel pipe continuous production line, the procedure that increases just means that Production Flow Chart prolongation, occupied ground increase, production efficiency reduce, also have input cost and maintenance cost to raise more.If remove surface treatment link in the workshop section of spraying paint of steel pipe's production, considerable economic benefit will be formed.Realize sticking power good on not surface treated steel pipe, will consider that when ultraviolet-curing paint formulating of recipe paint liquid is to the dissolving of grease and the infiltration to steel surface rusty scale.Because steel pipe can use oils or grease in the course of processing; such as, in the pipe cutting operation of weldless steel tube is produced, raise the efficiency in normally used oil or grease; or use to prevent from abrading straightening roll, so steel tube surface has greasy dirt usually in pipe aligning operation.On the other hand steel pipe transmission and deposit in process and can get rusty.
Therefore, prepare a kind of for steel pipe temporary protection, without the need to the UV-curing coating of surface treatment (there is greasy dirt and corrosion), there is very strong realistic meaning.
Summary of the invention
Technical problem to be solved by this invention is: in prior art; before the steel that there is greasy dirt and corrosion at effects on surface carries out supercoat coating; need to carry out surface preparation to steel; on steel production line; many increases by one pretreatment process; Production Flow Chart can be extended, reduce production efficiency, and increase cost.
For solving this technical problem, the invention provides a kind of for steel surface, free radical initiation type ultraviolet-curing paint, this coating, when not carrying out rust cleaning except wet goods pre-treatment, also can form good adhesion effect.
The component of this ultraviolet-curing paint calculates by weight, is respectively:
Urethane acrylate oligomer 36%-55%
Acrylic ester monomer 35%-50%
Metal adhesion promotor 1%-3%
Non-reactive sticking power promotes resin 1%-3%
Corrosion contacting permeation agent 1%-2.5%
Light trigger 3%-10%
Flow agent 0.1%-0.5%
Defoamer 0.1%-0.5%
Wherein, urethane acrylate oligomer selects the mixture of one or more of difunctionality and polyfunctionality urethane acrylate oligomer, and, the second-order transition temperature of the urethane acrylate oligomer selected is 5 DEG C-30 DEG C, if as the second-order transition temperature of the urethane acrylate oligomer of main body lower than at 5 DEG C, so water molecules can easily permeate and be diffused into the cured film of obtained coating composition, thus reduces the rust-preventing characteristic of film.
On content, if the consumption of urethane acrylate oligomer is less than 36 parts, so the overall activity of coating is on the low side, and curing speed is slack-off, possibly cannot meet the quick-setting requirement of paint line; If consumption is greater than 55 parts, so coating will be not suitable for spraying because viscosity is too high, and the levelling of this rustproof lacquer is by influenced.
Acrylic monomer is monoesters and diester, first need when selecting monoesters to consider that monomer is to the solvency power of oligopolymer from solubility parameter, if the solubility parameter of oligopolymer is beyond monomer solubility parameter area, so the consistency of monomer and oligopolymer can be deteriorated, paint liquid turbid appearance, oligopolymer is easily separated out.The selection of monomer also will consider volumetric shrinkage and surface tension, and the monomer of low surface tension is beneficial to coating effectively sprawling on metal base, and the low solidification process floating coat that can reduce of volumetric shrinkage shrinks the loss of adhesion problem brought.As preferably: acrylic monomer is selected from Isooctyl acrylate monomer, acrylate, isobornyl acrylate, ring TriMethylolPropane(TMP) methylal acrylate, propylene glycol diacrylate or tripropylene glycol diacrylate.
Above-mentioned metal adhesion promotor is phosphoric acid ester adhesion promoter, comprises simple function, difunctionality acid esters.The industry trade mark comprises CD9050, CD9051, SR9016.
As preferably: non-reacted sticking power promotes that resin is selected from simultaneously containing hydroxyl and epoxy group(ing), be liquid resin at normal temperatures, as epoxy resin 6101, this resinoid solubility parameter is similar with grease, have the oil of steel tube surface and necessarily help solvency action, the sticking power of coating to band oil place steel pipe can be improved.The more important thing is the strong polar hydroxyl groups that non-reactive resin contains and permeate agent with the use of time, significantly can promote the sticking power of coating to steel pipe corrosion position.
As preferably: permeate agent is one or both composition of kerosene and pimelinketone, and pimelinketone and kerosene are used in the formula of photo-cured coating by the present invention first, very well the sticking power of photo-cured coating at corrosion steel surface must be solved.When permeate agent add-on is greater than 2.5%, the time of drying of coating obviously can be extended, in order to the object consumption reaching instantaneous solidification preferably controls below 2.5%; On the contrary, when consumption is less than 1%, osmosis will do not had.
In above-mentioned formula, the free radical photo-initiation of involved light trigger to be absorbing wavelength be 240-360nm, this absorption bands have matched the emission wavelength of current industrial high voltage mercury lamp preferably.Light trigger is selected from 1-hydroxy cyclohexyl phenylketone (the industrial trade mark 184), 2-hydroxy-2-methyl-1-phenyl-acetone (the industrial trade mark 1173), two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (the industrial trade mark 819).
If the consumption of initiator in formula is greater than 10%, so initiator all can not participate in reaction at Light Curing, remaining light trigger will remain in film, when film is when exterior exposures is under sunlight, they can absorb the ultraviolet in sunlight thus decompose and produce free radical, and free radical will cause the aging of film.If light-initiated dosage is less than 3%, so system does not have enough free radicals to carry out initiated polymerization solidification at short notice, can not meet the requirement of high linear speed during steel pipe's production.
The effect of flow agent reduces diagram of system surface tension, and reduce shrinkage cavity and occur, flow agent is selected from BYK-306, BYK-373, HX-3010.
The bubble in coating is eliminated in the effect of defoamer, and ensure the quality of the rear film of construction, defoamer is selected from BYK-055, HX-2100 or HX-2000.
Present invention also offers a kind of preparation method of above-mentioned ultraviolet-curing paint.Concrete preparation process is: urethane acrylate oligomer, acrylic ester monomer, adhesion promoter, sticking power are promoted resin, permeate agent, light trigger, flow agent and defoamer, after weighing by weight percentage, at 40-50 DEG C, fully stir in Scattered Kettle, each component is mixed, filters with fie screen and obtain ultraviolet-curing paint.
In preparation process, need ensure by above-mentioned formula ratio and making method, the ultraviolet-curing paint total acid value of preparation is greater than 6mg/g(potassium hydroxide-ethanol solution volumetry).
The invention has the beneficial effects as follows: ultraviolet-curing paint prepared by the present invention, the non-reacted resin introduced in photo-cured coating system and corrosion permeate agent, play synergistic effect, efficiently solve steel tube surface greasy dirt rusty stain to the disadvantageous effect of photo-cured coating sticking power.This coating can directly be covered with paint, lacquer, colour wash, etc. on the steel that surface exists oil stain and rust stain, and steel, without the need to the pretreatment procedure through degreasing and rust removal, simplify production technique, have saved cost.Coating adhesion≤1 grade (cross-hatching measures according to GB/T9286-1998) after solidification.
Accompanying drawing explanation
Fig. 1 is on actual production line, and the state of appearance before the application of band rust steel pipe, can find out that these steel pipes have reached certain corrosion degree.
Fig. 2 is on actual production line, the state of appearance after the application of band rust steel pipe.
Embodiment
Embodiment 1
By weight: Sartomer's trade mark is the urethane acrylate oligomer 45 parts of CN981; Isobornyl acrylate 21 parts, acrylate 9 parts, Isooctyl acrylate monomer 12 parts; 3 parts of adhesion promoter CD9051; Light trigger 1-hydroxy cyclohexyl phenylketone (the industrial trade mark 184) 5 parts; 2 parts of epoxy resin 6101s; Kerosene 2.5 parts; 0.25 part of flow agent BYK-306; 0.25 part of defoamer BYK-055.
By above-mentioned weight ratio, each component fully stirred in the Scattered Kettle of the band heating unit of 40-50 DEG C, each component is mixed, with 120 object fie screens, namely double filtration obtains ultraviolet-curing paint.
According to potassium hydroxide-ethanol solution titration measuring, gained coating acid value is 6.2, is coated on without any surface-treated, and on the surface with oil stain and rust stain, H-40 level steel petroleum casing pipes surface, at 500mj/cm
2energy under solidify, after completion of cure, coat-thickness is 50 μm, and by cross-hatching, measuring the sticking power of coating according to GB/T9286-1998 is 0 grade.
Embodiment 2
By weight: Sartomer's trade mark is the urethane acrylate oligomer 46 parts of CN963; Isobornyl acrylate 22 parts, acrylate 8 parts, Isooctyl acrylate monomer 7 parts, propylene glycol diacrylate 2 parts; CD9050 adhesion promoter 3 parts; 8 parts of light trigger 2-hydroxy-2-methyl-1-phenyl-acetones (the industrial trade mark 1173); 1.5 parts of epoxy resin 6101s; Pimelinketone 1.8 parts; 0.35 part of flow agent BYK-373; 0.35 part of defoamer HX-2100.
By above-mentioned weight ratio, each component fully stirred in the Scattered Kettle of the band heating unit of 40-50 DEG C, each component is mixed, with 120 object fie screens, namely double filtration obtains ultraviolet-curing paint.
According to potassium hydroxide-ethanol solution titration measuring, gained coating acid value is 6.8, is coated on without any surface-treated, and on the surface with oil stain and rust stain, J-55 level steel petroleum casing pipes surface, at 400mj/cm
2energy under solidify, after completion of cure, coat-thickness is 50 μm, and by cross-hatching, measuring the sticking power of coating according to GB/T9286-1998 is 1 grade.
Embodiment 3
By weight: Sartomer's trade mark is the urethane acrylate oligomer 43 parts of CN965; Isobornyl acrylate 20 parts, acrylate 10 parts, Isooctyl acrylate monomer 7 parts, tripropylene glycol diacrylate 5 parts; SR9016 adhesion promoter 2.7 parts; 9 parts of two (2,4,6-trimethylbenzoyl) phenyl phosphine oxides (the industrial trade mark 819) of light trigger; 1.8 parts of epoxy resin 6101s; Kerosene 1 part; 0.25 part of flow agent HX-3010; 0.25 part of defoamer HX-2000.
By above-mentioned weight ratio, each component fully stirred in the Scattered Kettle of the band heating unit of 40-50 DEG C, each component is mixed, with 120 object fie screens, namely double filtration obtains ultraviolet-curing paint.
According to potassium hydroxide-ethanol solution titration measuring, gained coating acid value is 7.1, is coated on without any surface-treated, and on the surface with oil stain and rust stain, N-80 level steel petroleum casing pipes surface, at 500mj/cm
2energy under solidify, after completion of cure, coat-thickness is 50 μm, and by cross-hatching, measuring the sticking power of coating according to GB/T9286-1998 is 1 grade.
Comparative example 1(is compared to formula of the present invention, and the content of corrosion contacting permeation agent kerosene increases):
By weight: Sartomer's trade mark is the urethane acrylate oligomer 44.5 parts of CN981; Isobornyl acrylate 21 parts, acrylate 9 parts, Isooctyl acrylate monomer 12 parts; 3 parts of adhesion promoter CD9051; Light trigger 1-hydroxy cyclohexyl phenylketone (the industrial trade mark 184) 5 parts; 2 parts of epoxy resin 6101s; Kerosene 3 parts; 0.25 part of flow agent BYK-306; 0.25 part of defoamer BYK-055.
By above-mentioned weight ratio, each component fully stirred in the Scattered Kettle of the band heating unit of 40-50 DEG C, each component is mixed, with 120 object fie screens, namely double filtration obtains ultraviolet-curing paint.
According to potassium hydroxide-ethanol solution titration measuring, gained coating acid value is 6.1, is coated on without any surface-treated, and on the surface with oil stain and rust stain, H-40 level steel petroleum casing pipes surface, uses 500mj/cm
2the UV-irradiation of energy, can not get solidification for a long time.
Comparative example 2(is compared to formula of the present invention, and the content of corrosion contacting permeation agent pimelinketone increases):
By weight: Sartomer's trade mark is the urethane acrylate oligomer 44.8 parts of CN963; Isobornyl acrylate 22 parts, acrylate 8 parts, Isooctyl acrylate monomer 7 parts, propylene glycol diacrylate 2 parts; CD9050 adhesion promoter 3 parts; 8 parts of light trigger 2-hydroxy-2-methyl-1-phenyl-acetones (the industrial trade mark 1173); 1.5 parts of epoxy resin 6101s; Pimelinketone 3 parts; 0.35 part of flow agent BYK-373; 0.35 part of defoamer HX-2100.
By above-mentioned weight ratio, each component fully stirred in the Scattered Kettle of the band heating unit of 40-50 DEG C, each component is mixed, with 120 object fie screens, namely double filtration obtains ultraviolet-curing paint.
According to potassium hydroxide-ethanol solution titration measuring, gained coating acid value is 6.6, is coated on without any surface-treated, and on the surface with oil stain and rust stain, J-55 level steel petroleum casing pipes surface, at 400mj/cm
2energy under solidify, after completion of cure, coat-thickness is 50 μm, and by cross-hatching, measuring the sticking power of coating according to GB/T9286-1998 is 2 grades.
Comparative example 3(is compared to formula of the present invention, and the content of corrosion contacting permeation agent kerosene reduces):
By weight: Sartomer's trade mark is the urethane acrylate oligomer 43 parts of CN965; Isobornyl acrylate 20 parts, acrylate 12 parts, Isooctyl acrylate monomer 5 parts, tripropylene glycol diacrylate 5 parts; SR9016 adhesion promoter 3 parts; 9 parts of two (2,4,6-trimethylbenzoyl) phenyl phosphine oxides (the industrial trade mark 819) of light trigger; 1.8 parts of epoxy resin 6101s; Kerosene 0.7 part; 0.25 part of flow agent HX-3010; 0.25 part of defoamer HX-2000.
By above-mentioned weight ratio, each component fully stirred in the Scattered Kettle of the band heating unit of 40-50 DEG C, each component is mixed, with 120 object fie screens, namely double filtration obtains ultraviolet-curing paint.
According to potassium hydroxide-ethanol solution titration measuring, gained coating acid value is 7.3, is coated on without any surface-treated, and on the surface with oil stain and rust stain, N-80 level steel petroleum casing pipes surface, at 500mj/cm
2energy under solidify, after completion of cure, coat-thickness is 50 μm, and by cross-hatching, measuring the sticking power of coating according to GB/T9286-1998 is 3 grades.
Comparative example 4(, compared to formula of the present invention, does not add non-reactive sticking power and promotes resin):
By weight: Sartomer's trade mark is the urethane acrylate oligomer 47 parts of CN981; Isobornyl acrylate 21 parts, acrylate 9 parts, Isooctyl acrylate monomer 12 parts; 3 parts of adhesion promoter CD9051; Light trigger 1-hydroxy cyclohexyl phenylketone (the industrial trade mark 184) 5 parts; Kerosene 2.5 parts; 0.25 part of flow agent BYK-306; 0.25 part of defoamer BYK-055.
By above-mentioned weight ratio, each component fully stirred in the Scattered Kettle of the band heating unit of 40-50 DEG C, each component is mixed, with 120 object fie screens, namely double filtration obtains ultraviolet-curing paint.
According to potassium hydroxide-ethanol solution titration measuring, gained coating acid value is 6.4, is coated on without any surface-treated, and on the surface with oil stain and rust stain, H-40 level steel petroleum casing pipes surface, at 500mj/cm
2energy under solidify, after completion of cure, coat-thickness is 50 μm, and by cross-hatching, measuring the sticking power of coating according to GB/T9286-1998 is 4 grades.
Comparative example 5(, compared to formula of the present invention, does not add the agent of corrosion contacting permeation):
By weight: Sartomer's trade mark is the urethane acrylate oligomer 47.8 parts of CN963; Isobornyl acrylate 22 parts, acrylate 8 parts, Isooctyl acrylate monomer 5.5 parts, propylene glycol diacrylate 2 parts; CD9050 adhesion promoter 3 parts; 8 parts of light trigger 2-hydroxy-2-methyl-1-phenyl-acetones (the industrial trade mark 1173); 3 parts of epoxy resin 6101s; 0.35 part of flow agent BYK-373; 0.35 part of defoamer HX-2100.
By above-mentioned weight ratio, each component fully stirred in the Scattered Kettle of the band heating unit of 40-50 DEG C, each component is mixed, with 120 object fie screens, namely double filtration obtains ultraviolet-curing paint.
According to potassium hydroxide-ethanol solution titration measuring, gained coating acid value is 6.6, is coated on without any surface-treated, and on the surface with oil stain and rust stain, J-55 level steel petroleum casing pipes surface, at 400mj/cm
2energy under solidify, after completion of cure, coat-thickness is 50 μm, and by cross-hatching, measuring the sticking power of coating according to GB/T9286-1998 is 4 grades.
Claims (3)
1. a free radical initiation type ultraviolet-curing paint, is characterized in that: the composition of described ultraviolet-curing paint, is by weight percentage
Described non-reactive sticking power promotes that resin is the epoxy resin 6101 simultaneously containing hydroxyl and epoxy group(ing).
2. ultraviolet-curing paint as claimed in claim 1, is characterized in that: described corrosion contacting permeation agent is one or both composition of kerosene and pimelinketone.
3. the preparation method of the ultraviolet-curing paint as described in any one of claim 1 to 2, it is characterized in that: the concrete steps of described method are, urethane acrylate oligomer, acrylic ester monomer, adhesion promoter, sticking power are promoted resin, permeate agent, light trigger, flow agent and defoamer, after weighing by weight percentage, at 40-50 DEG C, fully stir in Scattered Kettle, each component is mixed, filters with fie screen and obtain ultraviolet-curing paint.
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| CN103849315A (en) * | 2014-02-28 | 2014-06-11 | 天津大学 | Polydimethylsiloxane cured antirust paint and preparation method thereof |
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| CN101280154A (en) * | 2007-04-06 | 2008-10-08 | 上海海优威电子技术有限公司 | Ultraviolet curing vacuum metallizing coating |
| CN101837667A (en) * | 2010-04-27 | 2010-09-22 | 惠州市嘉淇涂料有限公司 | Ultraviolet cured coating and application thereof |
| CN102585157A (en) * | 2012-03-13 | 2012-07-18 | 广东深展实业有限公司 | Ultraviolet light polymerization polyfunctionality polyurethane acrylate vacuum coating surface coating resin |
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| CN101280154A (en) * | 2007-04-06 | 2008-10-08 | 上海海优威电子技术有限公司 | Ultraviolet curing vacuum metallizing coating |
| CN101837667A (en) * | 2010-04-27 | 2010-09-22 | 惠州市嘉淇涂料有限公司 | Ultraviolet cured coating and application thereof |
| CN102585157A (en) * | 2012-03-13 | 2012-07-18 | 广东深展实业有限公司 | Ultraviolet light polymerization polyfunctionality polyurethane acrylate vacuum coating surface coating resin |
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Denomination of invention: The invention relates to an ultraviolet curing coating for steel surface and a preparation method thereof Effective date of registration: 20210928 Granted publication date: 20150826 Pledgee: Industrial and Commercial Bank of China Limited Changzhou Economic Development Zone sub branch Pledgor: JIANGSU LANLING POLYMER MATERIAL Co.,Ltd. Registration number: Y2021980010096 |